CN114751887A - Synthetic method of cyclic ethane carbonic ester - Google Patents
Synthetic method of cyclic ethane carbonic ester Download PDFInfo
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- CN114751887A CN114751887A CN202210425738.7A CN202210425738A CN114751887A CN 114751887 A CN114751887 A CN 114751887A CN 202210425738 A CN202210425738 A CN 202210425738A CN 114751887 A CN114751887 A CN 114751887A
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- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 33
- 150000002148 esters Chemical class 0.000 title claims abstract description 23
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000010189 synthetic method Methods 0.000 title description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 213
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 41
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 35
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 32
- MMEZEOFKMBMDGP-UHFFFAOYSA-N C(O)(O)=O.CC Chemical compound C(O)(O)=O.CC MMEZEOFKMBMDGP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 12
- -1 alkali metal alkoxide Chemical class 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000000066 reactive distillation Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- ZSWYLHOVUYJAGZ-UHFFFAOYSA-N 1,3-dioxaspiro[3.5]nonan-2-one Chemical compound C1(OC2(CCCCC2)O1)=O ZSWYLHOVUYJAGZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000010408 film Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing ethylene carbonate, which takes a reaction rectifying tower as a reaction site, dimethyl carbonate and ethylene glycol are subjected to ester exchange continuously in the reaction rectifying tower under the action of a catalyst to obtain methanol at the tower top, and a mixture of the ethylene glycol, the ethylene carbonate and the catalyst is extracted at the tower bottom. Then the catalyst is recycled, the cyclic ethane carbonic ester is separated and refined, and the ethylene glycol is recycled. Compared with the prior art, the method has the advantages of simple process flow for separating the catalyst and the product, high production continuity, suitability for large-scale production and equipment cost saving.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a synthetic method of cyclic ethane carbonic ester.
Background
The cyclic ethane carbonic Ester (EC) is a solvent with excellent performance and an organic synthesis intermediate, and is widely applied to industries such as battery electrolyte, ester intermediates, fibers, pharmacy, organic synthesis and the like. The EC can be synthesized by phosgene method, urea alcoholysis method, and ethylene oxide and carbon dioxide addition method. The phosgene process was the earliest method for the industrial preparation of cyclic ethane carbonate and was eliminated due to the extreme toxicity of phosgene and the severe environmental pollution. The urea alcoholysis method also has the problems of urea decomposition, difficult catalyst recovery and the like at present, and is still in the research stage at present. The atom utilization rate of ethylene oxide and carbon dioxide in the ethylene oxide method reaches 100 percent, which is the main process for industrially producing ethylene carbonate at present, however, the ethylene oxide is expensive and has higher production cost, and the ethylene oxide is flammable and explosive and is difficult to transport, and the industrial production is greatly influenced by the production area of raw materials. The transesterification reaction is gradually regarded as important because of its mild reaction conditions and high safety.
The patent CN 109438410A discloses a MgO/NaY solid base catalyst used for the transesterification of dimethyl carbonate (DMC) and Ethylene Glycol (EG) to synthesize cyclic ethane carbonate, the reaction temperature is 90-120 ℃, the reaction time is 2-12h, and the catalyst dosage is 5-45% of ethylene glycol. After the catalyst is circulated for five times, the activity of the catalyst is reduced from 94.4 percent of the first reaction to 91.4 percent, and the problems of long reaction time, large catalyst consumption and high price exist, and the activity of the catalyst needs to be further improved. There is still a need to develop an economical and efficient catalytic process for the transesterification synthesis process.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing cyclic ethane carbonate.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a method for synthesizing cyclohexane carbonate, which takes dimethyl carbonate and ethylene glycol as raw materials, synthesizes the cyclohexane carbonate by an ester exchange method, and produces methanol as a byproduct.
In one embodiment of the present invention, the method specifically comprises the steps of:
the reaction rectifying tower is used as a reaction site, dimethyl carbonate and ethylene glycol are subjected to ester exchange continuously in the reaction rectifying tower under the action of a catalyst, methanol is obtained at the tower top, and a mixture of ethylene glycol, ethylene carbonate and the catalyst is obtained at the tower bottom.
In one embodiment of the invention, the reactive distillation column is divided into a first section, a second section and a third section from top to bottom, the first section is a distillation section, the second section and the third section are reaction sections, the raw material ethylene glycol and the catalyst are fed from the first section to the second section, and the raw material dimethyl carbonate is fed from the second section to the third section.
In one embodiment of the invention, the alkali metal alkoxide is dissolved in ethylene glycol or methanol.
In one embodiment of the invention, the alkali metal of the alkali metal alkoxide is sodium or potassium and the alcohol is methanol, ethanol or ethylene glycol, preferably methanol or ethylene glycol.
In one embodiment of the invention, the molar ratio of the feed ethylene glycol to dimethyl carbonate entering the reactive rectification column is between 1.0 and 3.0, preferably between 1.3 and 2.0.
In one embodiment of the present invention, in the reactive distillation column, the molar ratio of the alkali metal alkoxide to the ethylene glycol is in the range of 1: 500 to 1: 50, preferably 1: 200 to 1: 100.
in one embodiment of the present invention, the method specifically comprises the steps of:
(1) preparing a catalyst: dissolving the alkali metal alkoxide in raw material ethylene glycol or methanol to prepare a catalyst material;
(2) Ester exchange reaction: respectively feeding the raw materials of ethylene glycol, dimethyl carbonate and catalyst material into a reaction rectifying tower through respective feeding pumps, obtaining cyclic ethane carbonate and methanol through catalytic ester exchange reaction, enabling the methanol to upwards enter a rectifying area under the rectifying action, enabling the methanol to enter the tower top, enabling the methanol to flow back through a condenser, obtaining high-purity methanol at the tower top, enabling the cyclic ethane carbonate to downwards enter the tower bottom, and forming a tower bottom material with excessive ethylene glycol and catalyst;
(3) and (3) catalyst recovery and circulation: the material at the bottom of the tower enters a film evaporator, ethylene glycol and cyclohexane carbonate are quickly evaporated, the catalyst is concentrated and is sent to the catalyst preparation step through a catalyst circulating pump, and the catalyst material is prepared according to the proportion and is recycled;
(4) separation and purification of cyclic ethane carbonate: feeding the ethylene glycol and the ethylene carbonate steam obtained in the step (3) into a separation and refining tower of ethylene carbonate, obtaining high-purity ethylene carbonate at the bottom of the tower, and obtaining ethylene glycol at the top of the tower;
(5) and (3) recycling the ethylene glycol: and (4) recycling the ethylene glycol obtained from the step (4) to the reaction rectifying tower for recycling.
In one embodiment of the present invention, the reactive distillation column, the thin film evaporator and the cyclic ethane carbonate separation and purification column are operated under reduced pressure.
In one embodiment of the invention, the rectification column overhead reflux ratio is from 0.1 to 1, preferably from 0.1 to 0.5.
In one embodiment of the invention, the operating temperature of the bottom of the reactive distillation column is between 70 and 130 ℃, preferably between 80 and 110 ℃.
Compared with the prior art, the catalyst related by the method has high catalytic activity, good stability, high product yield, low price and repeated recycling. The method has the advantages of simple process flow for separating the catalyst and the product, high production continuity, suitability for large-scale production and equipment cost saving.
Drawings
FIG. 1 is a schematic diagram of a process for the synthesis of cyclic ethane carbonate in accordance with the present invention.
Reference numbers in the figures:
1. a glycol material; 2. a dimethyl carbonate feed; 3. an outlet pipeline of the catalyst configuration device; 4. an outlet pipeline of the ethylene glycol conveying pump; 5. an outlet pipeline of the dimethyl carbonate conveying pump; 6. an outlet pipeline of the catalyst conveying pump; 7. a material outlet at the top of the reaction rectifying tower; 8. a bottom material outlet of the reaction rectifying tower; 9. an outlet pipeline of the catalyst circulating pump; 10. a material outlet at the top of the thin film evaporator; 11. a material outlet at the bottom of the thin film evaporator; 12. a glycol circulation line; 13. a tower bottom outlet of the cyclohexane carbonate separation refining tower; A1. a glycol delivery pump; A2. a dimethyl carbonate transfer pump; A3. a catalyst and glycol mixed liquid delivery pump; A4. a catalyst circulation pump; B. a catalyst preparation tank; r1, a reaction rectifying tower; r2. thin film evaporator; and R3. a separation and purification tower for cyclic ethane carbonic ester.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
The invention provides a method for synthesizing ethylene carbonate, which has a process flow shown in figure 1 and specifically comprises the following steps:
(1) preparing a catalyst: dissolving the alkali metal alkoxide in raw material ethylene glycol or methanol to prepare a catalyst material;
(2) ester exchange reaction: the method comprises the following steps of enabling ethylene glycol material 1 to enter a reaction rectifying tower R1 through an ethylene glycol conveying pump A1 and an outlet pipeline 4 of the ethylene glycol conveying pump, enabling dimethyl carbonate material 2 to enter the reaction rectifying tower R1 through a dimethyl carbonate conveying pump A2 and an outlet pipeline 5 of the dimethyl carbonate conveying pump, enabling the catalyst material to enter a reaction rectifying tower R1 through an outlet pipeline 3 of a catalyst configuration device, a catalyst and ethylene glycol mixed liquid conveying pump A3 and an outlet pipeline 6 of the catalyst conveying pump, wherein the reaction rectifying tower R1 is divided into a first section, a second section and a third section from top to bottom, the first section is a rectifying section, the second section and the third section are reaction sections, feeding the ethylene glycol material and the catalyst from the first section to the second section, and feeding the raw material dimethyl carbonate from the second section to the third section. Ethylene glycol and dimethyl carbonate are subjected to catalytic ester exchange reaction to obtain cyclic ethane carbonate and methanol, under the rectification action, the methanol upwards enters a rectification zone, enters the top of a tower, is refluxed through a condenser, and is subjected to high-purity methanol at a material outlet 7 at the top of the reaction rectification tower, and the cyclic ethane carbonate downwards enters the bottom of the tower, forms a tower bottom material with excessive ethylene glycol and catalyst, and is discharged from a bottom material outlet 8 of the reaction rectification tower;
(3) And (3) catalyst recovery and circulation: the bottom material discharged from a bottom material outlet 8 of the reactive distillation tower enters a film evaporator R2, ethylene glycol and ethylene carbonate are quickly evaporated, and the ethylene glycol and ethylene carbonate steam is discharged from a material outlet 10 at the top of the film evaporator; the catalyst is concentrated and discharged from a material outlet 11 at the bottom of the thin film evaporator, and is sent to a catalyst preparation tank B through a catalyst circulating pump A4 and a catalyst circulating pump outlet pipeline 9, and is prepared into a catalyst material according to a proportion and is circulated to an outlet pipeline 3 of a catalyst preparation device for recycling;
(4) separation and purification of cyclic ethane carbonate: ethylene glycol and ethylene carbonate steam discharged from a material outlet 10 at the top of the thin film evaporator enter a ethylene carbonate separation and purification tower R3, high-purity ethylene carbonate is obtained at the bottom of the tower, the high-purity ethylene carbonate is discharged from an outlet 13 at the bottom of the ethylene carbonate separation and purification tower, and ethylene glycol is obtained at the top of the tower;
(5) and (3) recycling the ethylene glycol: and (3) recycling the ethylene glycol obtained from the step (4) to the reactive distillation column R1 for recycling through an ethylene glycol recycling line 12.
In the above process, the molar ratio of the raw material ethylene glycol to the dimethyl carbonate entering the reactive distillation column is between 1.0 and 3.0, preferably between 1.3 and 2.0. The molar ratio of alkali metal alkoxide to ethylene glycol is in the range of 1: 500 to 1: 50, preferably 1: 200 to 1: 100. the reaction rectifying tower, the film evaporator and the cyclic ethane carbonic ester separation refining tower are operated under reduced pressure. The reflux ratio of the top of the rectifying tower is 0.1-1, preferably 0.1-0.5. The operation temperature of the bottom of the reaction rectifying tower is 70-130 ℃, and preferably 80-110 ℃.
Example 1
Adopting the synthesis process flow of the cyclic ethane carbonate shown in the figure 1, weighing 10g of ethylene glycol and 14.5g of dimethyl carbonate to prepare a raw material liquid, uniformly mixing, adding the raw material liquid into the bottom of a reaction rectifying tower, raising the temperature to 70 ℃, adding 113mg of potassium methoxide to start reaction timing, and after reacting for 60min, performing qualitative and quantitative analysis on a liquid-phase material by adopting a gas chromatography, wherein the conversion rates of DMC and EG are 66.2 percent and 64.6 percent, and the selectivity of EC and ME is respectively 92.2 percent and 99.8 percent.
Example 2
Adopting the synthesis process flow of the cyclic ethane carbonate shown in the figure 1, weighing 10g of ethylene glycol and 14.5g of dimethyl carbonate to prepare a raw material liquid, uniformly mixing, adding the raw material liquid into the bottom of a reaction rectification tower, raising the temperature to 60 ℃, adding 113mg of potassium methoxide to start reaction timing, after reacting for 15min, taking a liquid-phase material, and carrying out qualitative and quantitative analysis by adopting a gas chromatography, wherein the conversion rates of DMC and EG are 66.8% and 65.2%, and the selectivity of EC and ME is 92.3% and 99.8% respectively.
Example 3
Adopting the synthesis process flow of the cyclic ethane carbonate shown in the figure 1, weighing 10g of ethylene glycol and 14.5g of dimethyl carbonate to prepare a raw material liquid, uniformly mixing, adding the raw material liquid into the bottom of a reaction rectifying tower, raising the temperature to 50 ℃, adding 113mg of potassium methoxide to start reaction timing, after reacting for 15min, taking a liquid phase material, and carrying out qualitative and quantitative analysis by adopting a gas chromatography, wherein the conversion rates of DMC and EG are 64.6 percent and 65.3 percent, and the selectivity of EC and ME is 93.4 percent and 99.8 percent respectively.
Table 1 shows the activity evaluation of examples 1 to 3 in a reactive distillation column, the molar ratio of dimethyl carbonate to ethylene glycol being 1, the catalyst being potassium methoxide (CH)3OK), the molar ratio of the amount of catalyst used to dimethyl carbonate is 1: 100, adopting total reflux for reaction, and analyzing components in a tower kettle by using gas chromatography.
TABLE 1 composition of transesterification products of EG with dimethyl carbonate under different conditions
Examples 4 to 6
The molar ratio of ethylene glycol to dimethyl carbonate is set to be 1, the reflux ratio at the top of the tower is 0.1, and the temperatures at the bottom of the tower are 78, 85 and 107.7 ℃, the equilibrium conversion rates of DMC are respectively 80.2%, 86.8% and 96.3%.
Examples 7 to 9
Setting the molar ratio of ethylene glycol to dimethyl carbonate as 1.5, the reflux ratio at the top of the tower as 0.1, the temperature at the bottom of the tower as 85, 95.6 and 105 ℃, and the equilibrium conversion rates of DMC as 93.5%, 97.5% and 98.8% respectively.
Examples 10 to 12
Setting the mol ratio of ethylene glycol to dimethyl carbonate as 2, the reflux ratio at the top of the tower as 0.1, and the temperatures at the bottom of the tower as 96.6, 100 and 104 ℃, the equilibrium conversion rates of DMC are respectively 98.3%, 98.7% and 99.0%.
Table 2 shows the results of examples 4 to 9.
TABLE 2 results of the transesterification synthesis of cyclic ethane carbonates
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for synthesizing the cyclic ethane carbonic ester is characterized in that dimethyl carbonic ester and ethylene glycol are used as raw materials, the cyclic ethane carbonic ester is synthesized by an ester exchange method, and a byproduct of methanol is generated.
2. The method for synthesizing the cyclic ethane carbonate as claimed in claim 1, wherein a reaction rectifying tower is used as a reaction site, dimethyl carbonate and ethylene glycol are subjected to ester exchange continuously in the reaction rectifying tower under the action of a catalyst, methanol is obtained at the tower top, and a mixture of the ethylene glycol, the cyclic ethane carbonate and the catalyst is extracted at the tower bottom.
3. The method for synthesizing the ethylene carbonate according to claim 2, wherein the reaction rectifying tower is divided into a first section, a second section and a third section from top to bottom, the first section is a rectifying section, the second section and the third section are reaction sections, the raw material ethylene glycol and the catalyst are fed between the first section and the second section, and the raw material dimethyl carbonate is fed between the second section and the third section.
4. The method for synthesizing cyclic carbonates according to claim 2, wherein the catalyst is an alkali metal alkoxide dissolved in ethylene glycol or methanol;
The alkali metal of the alkali metal alkoxide is sodium or potassium, and the alcohol is methanol, ethanol or glycol, preferably methanol or glycol.
5. The method for synthesizing the ethylene carbonate according to claim 2, wherein the molar ratio of the raw material ethylene glycol to the dimethyl carbonate entering the reactive distillation column is between 1.0 and 3.0, preferably between 1.3 and 2.0.
6. The method for synthesizing cyclic ethane carbonate according to claim 2, wherein the molar ratio of the alkali metal alkoxide to the ethylene glycol in the reactive distillation column is in the range of 1: 500 to 1: 50, preferably 1: 200 to 1: 100.
7. the method for synthesizing the cyclic ethane carbonate according to any one of claims 1 to 6, wherein the method specifically comprises the steps of:
(1) preparing a catalyst: dissolving the alkali metal alkoxide in raw material ethylene glycol or methanol to prepare a catalyst material;
(2) ester exchange reaction: respectively feeding the raw materials of ethylene glycol, dimethyl carbonate and catalyst material into a reaction rectifying tower through respective feeding pumps, obtaining cyclic ethane carbonate and methanol through catalytic ester exchange reaction, enabling the methanol to upwards enter a rectifying area under the rectifying action, enabling the methanol to enter the tower top, enabling the methanol to flow back through a condenser, obtaining high-purity methanol at the tower top, enabling the cyclic ethane carbonate to downwards enter the tower bottom, and forming a tower bottom material with excessive ethylene glycol and catalyst;
(3) And (3) catalyst recovery and circulation: the tower bottom material enters a film evaporator, ethylene glycol and cyclohexane carbonate are evaporated, the catalyst is concentrated and is sent to the catalyst preparation step through a catalyst circulating pump, and the catalyst is prepared into a catalyst material according to a proportion and recycled;
(4) separating and refining the cyclic ethane carbonic ester: feeding the ethylene glycol and the ethylene carbonate steam obtained in the step (3) into a separation and refining tower of ethylene carbonate, obtaining high-purity ethylene carbonate at the bottom of the tower, and obtaining ethylene glycol at the top of the tower;
(5) and (3) recycling the ethylene glycol: and (4) recycling the ethylene glycol obtained from the step (4) to the reaction rectifying tower for recycling.
8. The method for synthesizing cyclic ethane carbonate according to claim 7, wherein the reaction rectifying tower, the thin film evaporator and the cyclic ethane carbonate separation and purification tower are operated under reduced pressure.
9. The method for synthesizing ethylene carbonate according to claim 7, wherein the reflux ratio of the top of the rectifying tower is 0.1-1, preferably 0.1-0.5.
10. The method for synthesizing the cyclic ethane carbonate according to claim 7, wherein the operation temperature of the bottom of the reaction rectifying tower is 70-130 ℃, preferably 80-110 ℃.
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| CN108794300A (en) * | 2018-05-18 | 2018-11-13 | 岳阳昌德化工实业有限公司 | The Isolation method of raw material containing ethylene glycol and 1,2- butanediols and the preparation method of epoxy butane |
| CN109438410A (en) * | 2018-12-05 | 2019-03-08 | 常熟市常吉化工有限公司 | A kind of method of synthesizing ethylene carbonate |
| CN111116543A (en) * | 2019-12-26 | 2020-05-08 | 山西中科惠安化工有限公司 | Method and device for separating polyol and cyclic carbonate in urea and polyol reaction liquid |
| CN114478187A (en) * | 2022-02-21 | 2022-05-13 | 福州大学 | Process for coproducing methanol and ethylene carbonate through reaction and rectification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108794300A (en) * | 2018-05-18 | 2018-11-13 | 岳阳昌德化工实业有限公司 | The Isolation method of raw material containing ethylene glycol and 1,2- butanediols and the preparation method of epoxy butane |
| CN109438410A (en) * | 2018-12-05 | 2019-03-08 | 常熟市常吉化工有限公司 | A kind of method of synthesizing ethylene carbonate |
| CN111116543A (en) * | 2019-12-26 | 2020-05-08 | 山西中科惠安化工有限公司 | Method and device for separating polyol and cyclic carbonate in urea and polyol reaction liquid |
| CN114478187A (en) * | 2022-02-21 | 2022-05-13 | 福州大学 | Process for coproducing methanol and ethylene carbonate through reaction and rectification |
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